Aldehydo-substituted mono- and di-thiophosphoric acid esters



United States Patent 3,176,035 ALDEHYDO-SUBSTHTUTED MONO- AND DI-THIQPHOSPHORIC ACHD ESTERS Karl Lutz, Basel, and Max Schuler, Arlesheirn, Switzerland, assignors to Sandoz Ltd, Basel, Switzerland No Drawing. Filed July 14, 1960, Ser. No. 42,751 Claims priority, application Switzerland, lluly 17, 1959,

Claims. ici. 260-461) The present invention is concerned with new insecticidal and acaricidal monothiophosphoric and dithiophosv phoric acid esters.

The aforesaid new monothiophosphoric and dithiophosphoric acid esters correspond to the formula OY B40113 wherein each of R and R represents CH or C H R stands for methyl, ethyl or propyl, R stands for H, methyl, ethyl or propyl, and Y stands for an oxygen atom or a sulfur atom.

Compounds I can advantageously be prepared by reacting a compound of the formula wherein R and R have the precedingly-recited significances and X stands for halogen with a compound of the formula P s-z R (HI) wherein Y is as precedingly recited and Z is a cation. Where Z is H, the reaction is carried out in the presence of an acid-binding agent.

The reaction is advantageously carried out in a solvent such as acetone, methylethylketone, dioxane or Water or in an aliphatic or aromatic hydrocarbon or in a mixture of such solvents, at normal or slightly raised temperature.

Suitable compounds of Formula II are for example the chloroacetyl-N-alkyl-formamides such as chloroacetylN- methyl-formamide, chloroacetyl N ethyl-formamide, chloroacetyl-N-isopropyl-formamide, as well as oz-ChlOi'O- propionyl-N-methyl-formamide; also the corresponding bromo-compounds. These intermediates are themselves new compounds and are being claimed in a copending divisional application.

etc. l

The monothiophosphoric and dithiophosphoric acid esters I of the present invention are liquid at room temperature (about 20 to about C.). They are generally soluble in oils as Well as in organic solvents, and are easily emulsifiable in water. The new esters I are out standingly suitable for combating pests, more especially insects and spider mites (T etranychia'ae sp.), in the protection of plants. Some of the compounds I are distinguished by excellent systemic action,

As will hereinafter appear, the new compounds I are distinguished from known systemically acting insecticides by reduced toxicity to warm-blooded animals, while hav ing as good or better systemic action.

(1) ORAL TOXICITY OF ACTlVE SUBSTANCES L 50( g-) Formula of active ingredient of No. composition: White Rat mouse (CHaO)2PSSCHzCONHCH3 130 (CH30)2PSSC2H4SC2H5 (CH30 2P(O)SC2H4SC2H5 4i) (CH30)2P(S)SC2H4SC2H5 (technical mix- 64 ture of the thiono and thiolo forms). (CH3O)zPSSCHzCO-NCH3 210 CHO (Norm-Compositions l to 4 are commercial preparations available.

on the market; composition 5 is according to Example 1 of the present application.) a

(2) SYSTEMIC ACTION Potted spiderwort plants are each watered with 100 milliliters of an aqueous emulsion of the insecticide being tested in such manner that the emulsion comes in contact only with the root system of the plants.

On the next day, each plant has applied thereto 30 grasshoppers (Carausius morosus) in the 2nd larval stage.

The systemic-insecticidal action of the various insecticides is checked daily by counting the number of dead insects.

The observed results are characterized by indication of the mortality (in percent of the applied insect-s) after x days after the treatment (percent/x): I

In combating pests by means of the new monothio phosphoric and dithiophosphoric acid esters of Formula I, the latter are advantageously admixed with emulsifying agents, for example with liquid polyglycol others obtained from higher alcohols, mercaptans or alky-lpheno-ls by addi 1 ing on ethylene oxide, then emulsifying the mixture in Water, and applying the emulsion by spraying thereof onto the surfaces to be treated. Solution aids, such as suitable organic solvents, for example monoor poly -alcohols, ketones, aroma-tic hydrocarbons, mineral oils, etc., may be incorporated into the mixtures of ester 1 and emulsifying' agents. In order to produce water-suspend-ible pulverulent products, there may also be incorporated into the said mixtures, solid carriers such as talc, kaolin, kiesel- 'guhr, bentoni-te, etc. The liquid or pulverulent products are emulsified or dispersed in Water before lacing used, it being preferable that the resultant emulsions or dispersion-s should contain 0.005 to 0.2% by weight of ester I.

However, the new rnonothiophosphoric and dithiophosphoric acid esters I can also be used without emulsifiers, in which event the esters are advantageously admixed with adhesion promoting agents and inert carniers, such as talc,

kaolin, kieselguhr, 'bentonite, etc., or with a mixture of 0 such carriers, so that the product may be used as a dusting composition or scattering composition.

The use of the new esters I for combating insect and arachnid pests and compositions for this purpose are claimed in a copending. divisional application.

The following examples set forth presently preferred exemplary embodiments of the invention. Parts and percentages are by Weight unless otherwise indicated. The relationship of parts by Weight to parts by volume is the same as that between grams and milliliters. Temperatures arein degrees .centigrade.

' (A) Examples of the preparation of the intermediates of the formula 010x 0N-R3 The general method for the preparation of the intermediates of the preceding formula is as follows:

1 mol of an oc-ChlOI'OCQI'bOXYliC acid chloride of the formula R -CHCl-COOl is dissolved in trichloroethylene, after which 1 mol of formamide of the formula is stirred in dropwise'at about 80 in the "course of 1 to 2 hours. Stirring of the reaction mixture is then further continued at the saidtemperature until hydrogen chloride development has practically ceased.

. 7 EXAMPLE 1.

59 parts (=1 mol) of the compound of the formula CH NHCHO' are dissolved in 100 parts by volume of trichloroethylene and the resultant solution is stirred dropwise in the course of 1 to 2 hours into. a solution, heated to 80, of 112 parts (=1-moi) ofchloroacetic acid chloride in 200 parts by volume of trichloroethylene. Stirringis then continued for about one more hour at 80. The resultant reaction product of the formula and the formamide of the formula lSO-C H7NHCHO there is obtained the intermediate of the formula ClCHzC obi-0 117450 a boiling point Cl-calc., 21.7%; found, 21.1%.

which has n =l.4482.

EXAMPLE 4:

In similar manner, from chloroacetic acid chloride and the formamide of the formula n-C H NHCO there is obtained the intermediate of the formula ClOI'IzCON-C3H71D Boiling point: 7982/0.7 mm. n =1.47O2.

EXAMPLE 5 In analogous manner, from a-chloropropionic acid chloride CH CHC1COCl and the formamide of the formula CH NHCHO there is obtained the intermediate of theformula CH3CHC1C ONCHa which boils at 64-67 0.5 mm. n =1.4812. Cl -calc., 23.7%; found, 23.3%. N-calc., 9.36%; found, 9.46%.

(B) Examples of the preparation and use of the end products of the formula are stirred together for 4 hours in 300 parts by volume of, chloroform at about 55. The chloroform layer is then washedsuccessively with water, 5% aqueous, sodium bicarbonate solution and again with water. After.

drying the chloroform layer and distilling off the 'chloroform, there is obtained in an about yield the compound of the formula (011mm s s OH2CON-CH3 in the form of a yellow oil. n ?=1.5522. Pcalc., 12.0%; found, 12.1%. S-calc., 24.9%; found, 25.4%.

EXAMPLE 7 30 parts of the compound of the formula ClCHzC (3N 2 r HO and 37 parts of the compound of the formula CH O PSSNI-I are stirred together for 2 hoursin parts by volume of acetone at 50. After the addition of 6 00 parts by volume of water, the organic layer is extracted with chloroform, the chloroform extract washed successively with water, 5% aqueous sodium bicarbonate solution and again with water, and then dried. After distilling off the chloroform, there remains as residue in an about 85% yield the compound of the formula.

( B DEP S SCH2CON-CZH5 in the form of a yellow oil. n =1.5384-. Pcalc., 11.4%; found, 11.6%. S-calc., 23.6%; found, 24.4%.

5 EXAMPLE 8 33 parts of the compound of the formula C1CH2CON-CH(CH3)2 and 37 parts of the compound of the formula (CH O) PSSNH are stirred together for 4 hours in 200 parts by volume of dioxane at 60. After the addition of 1000 parts by volume of water, the organic layer is extracted with chloroform. After drying the chloroform extract and distilling off the chloroform, there is obtained in an about 80% yield the compound of the formula (o11 0 ziisGHwoN-omom CHO in the form of a yellow-brown oil. calc., 10.9%; found, 11.2%.

EXAMPLE 9 27 parts of the compound of the formula ClOHzCON-OH and 40 parts of the compound of the formula (C2H50)2i-SNB are stirred together for 2 hours in 200 parts by volume of acetone at 50. The acetone solution is then cooled and separated from precipitated NaCl by filtration. The acetone is distilled from the. filtrate, the residue taken up in ether, the ether solution washed with water and dried over sodium sulfate.

After distilling off the ether, there remains as residue in practically quantitative yield the compound of the formula fi ((321150) 2P S CI'IzC ON-OH:

V i HO n =1.4928. Pcalc., 11.5%; found, 11.2%. S- calc., 11.9%; found, 11.7%.

. EXAMPLE 10 41 parts of the compound of the formula (C2H50)2:i. -S'NH4 and 50 parts of the compound of the formula OH3OHC1CONCH3 are stirred together for 2 hours in 200 parts by volume of acetone at 50. After the addition of 1000 parts by volume of water, the organic layer is extracted with chloroform. After drying the extract and distilling off the chloroform, there is obtained in an about 75% yield the compound of the formula (CzHO)ziSCI-ICONOH3 H3 H0 in the form of a yellowish oil. n =1.5257. Ncalc., 4.7%; found, 4.9%. P--calc., 10.4%; found, 10.9%. S-calc., 21.9%; found, 21.8%.

EXAMPLE 11 In analogous manner (to that of Example there is obtained from the compound of the formula 1 water.

and the compound of theformula GH OHClCON-CJEI;

the compound of the formula (CHaOhi S CH2CONCH3 CH0 are admixed with 30 parts of isooctylphenyloctaglycolether and with 50 parts of a petroleum fraction which boils at 210-280, specific gravity (20) 0.92, a clear solution being obtained which is well emulsifiable in Such an emulsion, containing 0.05 to 0.1% of the said ester, effects a kill on all stages of spider mites, e.g. Tetranychus telarius, Paratetranychus pilosus, etc.

EXAMPLE 14 20 parts of the ester of the formula (Gmoni s 012120 ON-CzH4 are admixed with20 parts of laurylhexaglycolether and 60 parts of xylene, the resultant product being readily water-emulsifiable. An aqueous emulsion of this product, which emulsion contains 0.2% of the ester, is sprayed on aphis-infested potted plants (Cineraria, aster, chrysanthemurn). In a short time, all aphis are dead.

EXAMPLE 15 (a) By admixing 25 parts of the ester of the formula II (CH 0) P s omo oN-orn with 25 parts of diisohexyl-heptylphenylhexaglycolether, 25 parts of xylene and 25 parts of diethyleneglycol, a product is obtained which is well emulsifiable with Water. Potted spiderwort plants of a height of about 20 cm. are each watered with 100 milliliters of an aqueous emulsion of the said product, such emulsion containing 0.02% of the active ester, care being taken that no green parts of the plant are wetted. The next day, 30 grasshopper larvae (Carausius morosus), second stage, are applied to each plant. The larvae feed on the leaves and in this way also include in their nourishment the aforesaid active ester which has been taken in by the roots of the plants and transported to the leaves. At the end of 8 days, no living larvae remain; all are dead.

(b) An aqueous emulsion of the same product, containing 02% of active ester, is sprayed on aphis-infected plants of Erigeron Canadense, in such manner that only the bottom part of the plants (not roots) are contacted, while the upper part of the plants-where the aphis are-remains untreated. After two to three days, all aphis on'the not-directly treated upper part are dead.

Bean plants in the two-leaf stage and which are infested with Aphis fabae are sprayed with an aqueous emulsion of the same composition0.02% of active ester-whereupon, in a few hours, all the aphis have been killed.

EXAMPLE 16 A pulverulent product of good suspendability in water is obtained by intimately admixing parts of the ester of the formula OHO with 3 parts of tert. dodecylmercaptanundecaglycolether, 7 parts of powdered silica gel and 75 parts of kaolin. A suspension prepared from this mixture and containing 0.1% of the said ester, when sprayed on aphis, produces a complete kill in a few hours.

EXAMPLE 17 2 parts of the ester of the formula I 0 (czHsohl S CHQC ON OHQ are admixed with 98 parts of talc, and the mixture ground in a ball mill. The product is a dusting agent which, dusted in areas infested by cockroaches (Perz'planeta americana), effects a 100% kill in 24 to 48 hours of all of the latter which come into contact with the dust.

Having thus disclosed the invention what is claimed is: 1. A compound of the formula R1O\( R4 0 P S( JH-( J-I|WR3 R CHO wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R; is a group of the formula -C H wherein n is a numeral from 0 to 3 inclusive, and Y is a chalcogen with an atomic weight from 16.00 to 32.06.

2. A compound of the formula R10 S R4 R20 CHO 4. The compound of the formula (CH O) l SOH C OlTT-CH;

5. The compound of the formula (CHaOMl S-"CH2OON-C2II5 6. T he compound of theformula (Olihofii SCH;C oN-omona 7. The compound ofthe formula 0 (ozHsohl S--CI]zCON-CH 8. The compound of theformula zI-I OMl S-CHCON-CH3 H3 HO 9. The compound of the formula Ha H O 10. A compound of the-formula alkoxy S II P SC H CONalky1 alkoxy HO wherein the alkoxy groups have at most two carbon atoms and the alkyl group has at most three carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,656,360 10/53 Hagemeyer 260561 2,668,831 2/54 Tolkmith 260-461v 2,712,029 6/55 Wenkle 260-461 2,890,947 6/59 Annable et a1. 260461 X 2,915,429 12/59 Scherer 167-22 2,920,993 1/ 60 Fairchild 167-22 2,923,738 2/60 Williams 26056l 2,928,862 3/60 Willard et al 260-461 J 2,955,137 10/60 Mayhew 260561 2,959,608 11/60 Crouch et a1. 26O461 3,004,055 10/61 Perini et'al. 260461 OTHER REFERENCES I Einhorn et al.: Justus Liebigs Annalen Der Chemie, vol. 343,1 1). 282-284 .1905 CHARLES B. PARKER, PrimaryExaminer.

MORRIS O. WOLK, MORRIS LIEBMAN, JOSEPH P. BRUST, Examiners. v 

1. A COMPOUND OF THE FORMULA 